Monoazo dyestuffs insoluble in water



Patented May 21, 1940 UNITED STATES MONOAZO DYESTUFFS INSOLUBLE IN WATER Ernst Fischer, Ofienbach-on-the-Mai-n, Germany,

assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application December 17, 1938, Serial No. 246,503. In Germany December 18,

4 Claims.

The present invention relates to monoazo] dyestufis insoluble in water; more particularly,

.it relates to dyestuffs of the following general formula CO.NH.aryl

. wherein X1 means hydrogen, an alkyl-, alkoxy-, aralkoxy-, aryloXy-group or halogen; X2 and X3 mean hydrogen, an alkyl-, alkoxy-, aralkoxy-, aryloxy-group, halogen or the group R1 SO2N R2 always one of the two substituents X2 and X3, not both simultaneously, being the group R1 -S02N R1 being an aliphatic radical containing more than 2 carbon atoms, an aralkyl or a hydroaromatic radical, R2 being an alkyl, aralkl, aryl or a hydroaromatic radical, with the proviso that if R1 and R2 are simultaneously alkyl radicals, the stun of their carbon atoms must be at least 5, and these alkyl radicals may be connected in a heterocyclic ring system; and Z stands for a carbazole, diphenylene oxide or diphenylene sulfide radical.

I have found that valuable pigment dyestufis may be obtained by coupling the diazo compound from an amine of the general formula wherein X1 means hydrogen, an alkyl-, alkoxy-. aralkoxy-, aryloXy-group or halogen; X2 and X3 mean hydrogen, an alkyl-, alkoxy-, aralkoxy-, aryloxy-group, halogen or the group R1 -SO2N always one of the two substituents X2 and X2, not both simultaneously, being the group R1 being an aliphatic radical containing more than 2 carbon atoms, an aralkyl or a hydroaromatic radical, R2 being an alkyl, aralkyl, aryl or a hydroaromatic radical, with the proviso that if R1 and R2 are simultaneously alkyl radicals, the sum of their carbon atoms must be at least 5, and these alkyl radicals may be connected in a heterocyclic ring system, with an arylide of 2-hydroxycarbazole-S-carboxylic acid, 3-hydroxydiphenylene oxide-2-carboxylic acid or 3-hydroxydiphenylene sulfide-2-carboxylic acid, only such dyestuif components being used as do not contain any group lending solubility in water,

such as the sulfonic or carboxylic acid group.

The new dyestufi's yield generally brown tints which, depending upon the kind of the diazocompound used, extend to black-brown and have good properties of fastness. They are insoluble in water, but very easily soluble in many organic solvents, for instance, hydrocarbons, alcohols, esters, ketones and can be used for coloring these solvents as well as the lacquers prepared by means of these solvents such as nitroor acetylcellulose lacquers, films or plastic masses. They are also very suitable for coloring varnishes, candles and fats. Owing to the differentsubstituents present in the dyestufis the suitability of the organic solvents named varies, but the most suitable solvents may easily be ascertained by experiment. I

In comparison with the dyestuffs described in German Patents Nos. 551,880, 594,326 and 596,753, the dyestuffs obtainable by this invention are distinguished by their enhanced solubility in organic solvents so that they are very suitable for coloring bodies of the aforesaid kind, whereas the dyestuffs of the said'patents have either no solubility in organic solvents or a solubility too small for these purposes.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto:

(1) 32.8 grams of l-amino-4-ethoxybenzene- 5-sulfo-n-dibutylamide are diazotised in the usual manner. In order to bind the excess of mineral acid sodium acetate is added to the diazo-solution and the whole is stirred into a solution of 33.7 grams of 2-hydroXycarbazole-3- (carbonyl-1'-amino-4-chlorobenzene) in dilute caustic soda solution. When the coupling is finished the dyestuff formed is filtered with suction, washed well and dried. It is a brown powder ,,cellulose ester lacquers dark brown tints of good which dissolves easily in acetone, butyl alcohol and other organic solvents and colors cellulose ester lacquers vivid brown tints of good properties of fastness.

(2) 31.4 grams of 1-amino-2-methoxybenzene- 5-sulfo-n-dibutylamide are diazotised in the usual manner. The diaZo-solution is made neutral to Congo paper by means of sodium acetate. It is then introduced, while stirring, into a solui ion of 33.7 grams of 2-hydroxy-carbazole-3- (carbonyl-1-amino-4-chlorobenzene) in dilute caustic soda solution. The dyestuff formed is filtered with suction, washed Well and dried. It dissolves easly in butyl acetate, xylene and other organic solvents and colors lacquers fast brown tints, which are somewhat more reddish than those obtainable with the product of Example 1.

(3) A pigment dyestufi is prepared as described in Examples 1 and 2 from the diazopompound of 31.4 grams of l-amino-Z-methoxybenzene-5-sulfo-n-dibutylamide and 36.3 grams of 3-hydroxydiphenylene oxide-2-(carbonyl-1'- amino-2'.5'dimethoxybenzene). It dissolves easily in butyl acetate and xylene and colors fastness to light.

(4) By using in Example 2 instead of 31.4

obtained which colors the various organic solvents and the lacquers prepared therewith reddish brown tints.

(5) From the diazo-compound of 32.8 grams of 1-amino-4-ethoxybenzene-5sulfo-di-isobutylamide and 31.9 grams of 3-hydroxydiphenylene sulfide-Z-carbonyl-aminobenzene there is obtained, in the manner described in Examples 1 and 2, a brown pigment dyestuff which is easily soluble in organic solvents and colors cellulose ester lacquers very fast tints.

(6) The pigment dyestuff obtainable as described in Examples 1 and 2 from the diazocompound of 29.8 grams of l-amino-Z-methylbenzene-5-sulfo-di-isobutylamide and 33.7 grams of 2-hydroxycarbazole-3-(carbonyl-1'-amino-4'- chlorobenzene) is a brown powder, which dissolves easily in organic solvents, such as esters, alcohols and the like, and colors cellulose ester lacquers fast brown tints which are somewhat more yellowish than those obtainable with the product of Example 1.

The following table indicates a number of other mono-azo-dyestufis obtainable by this invention, which are likewise easily soluble in organic solvents and have good properties of fastness:

Diem-compound from- Ooupled with- Shade l-amino-2-methoxybenzcne-5-sulf0-piperidid9 l-amino-Lchlorobenzene-fi-sulfo-piperidide l-amlno-2-methylbenzene-S-snlfo-N-methyl-iso-amylamlde. 1-amino-2:5-diethoxy-benzenei-sulfo-n-dibutylamido.

l-amino-4-eth0xybenzenc-5-sulfo-n-dibutylamide. l-amin0-2ethoxybenzene-5-sulfO-di-isobutylamid l-nmino-Q-methylbenzcne-fi-sulio-di-isobutylamide. l-aminc-2.5-dimethoxybenzene-4-sulfo-n-dibutylam 1-aminobenzene-4-sulfo-N-(n) -butylanilidc l-amino-2-mcthoxybenzcnc-5-(sul1o-N-ethyl-l-aminonaphthalene) l-amu1o-2-methylbenzene-5-(sulf0-N-(n)-butylbenzylamide). l-amino-2-methoxybenzene-S-sullo-dibenzylamide l-amngof-methylbenzeuc-5-(sullo-N-benzylcyclo-hexylam e 2-hydroxycarbnz0le-3-(cal-bony1-l-amino-4 chlorobcnzene 3-hydroxydiphenylene oxide-Z- (carbonyl-l -amino-2.

5-dimethoxy-benzcnc) o Z-hydroxycarbazol zene Reddish brown.

Do. Yellowish brown. Brown.

Do. Ycllowish brown.

Do. Do.

Dark brown.

Yellowish brown. Dark brown. Yellowish brown. Violctish brown. Ycllowish brown.

Brown.

Yellowish brown.

Reddish brown. Yellowish brown.

n-dibutylarnine 33.4 grams of 1-amino-2-methoxybenzene-5-sulfo-N(n)-butyl-anilide, a dyestuff of similarly good properties of fastness is v, 2 l-amino-2-methoxybenzene-5-sulfo-N-benzylanilide Reddisll brown.

22 1-amin0-4-methylbenzene-5-sulfo-dicyclohexylamlde Yellowlsh brown.

23 l-amino-3-mcthylbcnzenc-isulto-n-dibutylamide 24 l-aminol-b enzyl0xybcnzenc-5-sulfo-n-dibutylamide rown- 25 l-amino-3-ehlorobeuzene-4-sulfo-n-dibuty1amide 26 l-amigo-2-methylbenzene-5-sulfo-N-methyl-(n)-buty1- Yellowlsh brown.

am: e. 27 1amigo-2-rnethoxybenzene-S-sulIo-N-ethyl-cyclohexyl- Brown. am: e.

28 l-aminobenzene-3-sulfo-di-isobutylamide Yel owish brown. 29 l-amino-Z-methylbenzene-5-sulf0-n-dibuty1amide 9 0 l-amino-Zfi-dimflthoxybenzene-4-su1fo-n-dibutylamide--. d0 Reddlsh brown. 31 l-amino-2-phenoxybenzene-5-sulfo n-dibntylemide 2-hydroxycarbazole- -(carbonyl-am1nobenzene) Brown. 32 l-amino-Z-mcthoxybenzene-5-sulfo-n-dibutylamide ..d0 D0- 33 1-amino-2'chlorobenzcnc-fi-sulfo-n-dibutylamide 0.... Yellowish brown. 34 l-amino-2-methoxybcnzene-5-sulfo-n-dibutylamide 3-hydroxyd1phcnylene oxide-2-(carbonylaminobengene) Brown. 35 l-aminoi-ethoxybenzene-li-sulfo-n-dibutylamide.. B-hydgfiIyrIiiphfn Iene oxide-Z-(carbonyl-1-ammo- Do.

nap a one 36 l-amino-2-mcthoxyhenzenc-5-sulfo-n-dibutylamide 3-hzfilrox%diphen)ylene sulfide-Z-(carbonyl-1-amino-2- Do.

e oxy enzene 37 .do 9-efihyl-thydroxycarbazole-3-(carbonyl-2-aminonaph- Do.

t aen 38 .-...do 2-hydroxycarbazole-3-(carbonyl-1-amin0-2-methy1- D0.

benzene-5-sulfonyl-diethyl amine) 3 1-am1n0-4-ethoxybenzcne-5-sulto-n-dibutylamide .do D0 40 l-nmino-E-methoxybenzenc-5-sulfn-n-dibutylamide 2-hydroxycarbaz0le-3-(carbonyl-1-amino-2-methoxy- Do.

benzene-5'-sulfonyl-n-dibutylamine) 41 ..-..d0 2-hydroxycarbazole-3-(carbonyl-l-aminobenzene-3'- Do.

earbonyl-dlethylamine) 42 d0 3-hydroxydiphenylene oxidc-Z-(carbonyl-l-amino-2- D0.

methoxybenzene-5-sulfonyl-diethylamine).

grams of 1ammo-Z-methoxybenzene-fi-sulfo- Since an ob ect of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

I claim:

1. The water-insoluble monoazo dyestufis of the following general formula:

wherein X1 stands for a member of the group consisting of hydrogen, alkyl, alkoxy, benzyloxy, phenoxy and halogen; X2 and X3 stand for members of the group consisting of hydrogen, alkyl, alkoxy, benzyloxy, phenoxy, halogen and the group R1 SOEN always one of the two substituents X2 and IQ, not both simultaneously, being the group R1 being a member of the group consisting of a aliphatic radical containing more than 2 carbon atoms, benzyl and a hydroaromatic radical, R2 being a member of the group consisting of alkyl, benzyl, aryl and a hydroaromatic radical, with the proviso that if R1 and R2 are simultaneously alkyl radicals, the sum of their carbon atoms must be at least 5, and these alkyl radicals may be connected in a piperidine ring, Z stands for a radical of the group consisting of carbazole, diphenylene oxide and diphenylene sulfide, and Y stands for a member of the group consisting of radicals of the benzene and naphthalene series, being insoluble in Water, but very easily soluble in organic solvents and yielding generally brown tints of good properties of fastness.

2. The water-insoluble monoazo dyestuff of the following formula:

C4Ha som (1i) C4110 OHaO- being insoluble in water, but very easily soluble in organic solvents and yielding reddish brown tints of good properties of fastness.

3. The water-insoluble monoazo dyestuff of the following formula:

SOzN (n) I OlHo OCH;

CHaO- being insoluble in water, but very easily soluble in organic solvents and yielding reddish brown tints of good properties of fastness.

4. The water-insoluble monoazo dyestuff of the following formula:

being insoluble in Water, but very easily soluble in organic solvents and yielding reddish brown tints of good properties of fastness.

ERNST FISCHER. 

